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Publication numberUS3265524 A
Publication typeGrant
Publication date9 Aug 1966
Filing date24 Jun 1965
Priority date8 Feb 1963
Also published asDE1301242B
Publication numberUS 3265524 A, US 3265524A, US-A-3265524, US3265524 A, US3265524A
InventorsIgnacio P Echeagaray
Original AssigneeIgnacio P Echeagaray
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Recording blank
US 3265524 A
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Description  (OCR text may contain errors)

Augf 9, 1966 l. P. ECHEAGARAY 3,265,524

RECORDING BLANK Filed June 24, 1965 C l n f3 n u IN VEN TOR. [6N/1cm P ECHEAGAM Y Afro/ways United States Patent O 3,265,524 RECORDING BLANK Ignacio P. Echeagaray, 4349 W. 132nd St., Cleveland, Ohio 44135 Filed June 24, 1965, Ser. No. 470,318 8 Claims. (Cl. 117-36.8)

The present application is a continuation-in-part of application Serial No. 257,208, field Feb. 8, 1963, now abandoned, which application was a continuation-in-part of application Serial No. 112,300, tiled vMay 24, 1961, and now abandoned.

The present invention relates to recording blanks and, more particularly, to a heat sensitive recording blank which may be marked by a heating stylus.

An object of the present invention is the provision of a new and improved heat sensitive recording blank comprising a base material having a heat sensitive coating including polyvinylidene chloride, which coating is engageable with a heating stylus and upon engagement with the stylus decomposes at a relatively low temperature in a short time to provide a clear, sharp mark on the blank, and which decomposes before it melts permitting the stylus to move at a relatively high velocity without sticking.

A further object of the present invention is the provision of a new and improved recording blank having an indefinite storage life since it is highly resistant to acidity, humidity, and abrasion and is normally unaffected by atmospheric conditions.

i Another object of the present invention is to provide a highly sensitive recording blank comprising a base material having a coating including polyvinylidene chloride, wherein the coating is provided with a color t-o contrast with the color of a mark formed on the blank by engaging the coating with a heating stylus which decomposes the coating. A

A further object of the present invention is the provision of a highly sensitive recording blank, as noted in the next preceding paragraph, wherein suitable reagents are includedin the coating to aid in the decomposition thereof when the coating is engaged by the heating stylus.

A further object of the present invention is the provision of a recording blank, asrnoted in the next preceding paragraph, wherein the reagents may include zinc oxide and preferably zinc chloride, and wherein the zinc chloride dissolves the zinc oxide to provide very small particle sizes which greatly facilitate and aid decomposition of the coating by establishing more intimate physical contact between molecules of the reagents and the polyvinylidene chloride. Y v

A still further object of the present invention is the provision of a new and improved easily manufactured recording blank comprising a base material with a coating of polyvinylidene chloride thereon, wherein the coating is easily and uniformly applied to the base.

Applicant is aware of prior art attempts to provide `a heat sensitive paper having Va coating which includes lpolyvinyl chloride. vover a polyvinyl chloride coating. The use of a poly- Applicants coating has advantages Vinyl chloride coating providesa blank wherein the temperature at which a heating sstylus can mark the blank is relatively high when compared to the temperature at which a polyvinylidene chloride coating, asprovided herein, is marked. Since applicants coating containing t polyvinylidene chloride can be marked at a lower temperature than known coatings containing polyvinyl chloride, a sharper, clearer mark is achieved because the amount of other materials included in the iinal'product which burn is minimized and less sludge is produced to .interfere with the sylus. Moreover, the marking stylus ice can move faster over applicants polyvinylidene chloride coating since the temperature at which a mark is achieved is lower, and also because the coating does not soften before it decomposes, in which event the stylus tends to stick or drag. Thus, the stylus is able to move at a faster velocity, and an even sharper line is provided.

Further objects and advantages of the present invention will be apparent to those skilled in the art to which the invention relates from the following detailed description of a preferred embodiment made with reference to the drawings which form a part of this specification, and in which,

FIG. 1 is a perspective view of a recording blank embodying the present invention and a stylus adapted to mark the blank; and

FIG. 2 is an enlarged sectional view of the recording blank of FIG. 1 taken on the section line 2-2 of FIG. 1.

Referring to the drawings, the present invention is shown as embodied in a recording blank A which is adapted to be mlarked by Ia heating stylus B. The blank A includes a base materical C and a heat sensitive coating 12 on the base material and which decomposes or carbonizes to provide a mark on the blank when the stylus B engages the coating 12.

The bvase C of the blank is preferably electrically conductive, and in the illustrated embodiment comprises a strip of aluminum 13 laminated to a strip of paper 14. The base may alternatively, and preferably does, comprise \a zinc plate which aids the decomposition or carboniziation of the coating when engaged by a heating stylus, as will be discussed hereinbelow. Many other conventional and well known materials may be utilized for the base of thebl-ank such as paper impregnated with carbon, metal foils, etc.

The coating 12 includes vinylidene chloride, and may be polyvinylidene chloride alone. Prefenably the coating includes a copolymer of vinylidene chloridev -and acrylonitrile. Suitable materials forming decomposing or carbonizing aids or reagents are also prefenably included in the coating material and are discussed more fully hereinbelow.

The coating 12 is formed of a number of materials which are mixed to form a coating mixture which is applied to the base C. These materials preferably include a copolymer of vinylidene chloride vwith acrylonitrile, as mentioned above, reagents including preferably zinc oxide and Zinc chloride, and a suitable vollatile solvent. Preferably, acetone is used as the solvent but ethyl acetate or methyl ethyl ketone could also be used as the solvent. Also, suitable additional solvents could be used, such as toluene, propyl alcohol, etc., which control the rate of evaponation of the more volatile solvent.

The following table contains the relative quantities of each of the materials which preferably are included in the coating mixture and the preferred range of the percentage of each ingredient by weight:

The proportions of the ingredients set forth in the above table :are preferred land Imay be varied. The amount of solvent can be changed to provide `la coating of the desired viscosity for easy application, and the amounts of zinc oxide, zinc chloride, and copolymer of vinylidene chloride with acrylonitrile can be changed to change the Vthey are mixed and dissolves the zinc oxide.

stirred for about two hours at room temperature.

timbres.

contnast between the coating and the mark made by the stylus and to change the eciency of the marking operation, as will be discussed hereinbelow. However, if the amount of zinc chloride becomes too great the shelflife of the coating will be shortened.

The most desirable method ofV making the coating mixture begins with weighing the zinc oxide :and the acetone and pouring them into `a mixture vessel. The zinc chloride is then added to the zinc oxide and acetone mixture vwhile the mixture is being stirred. Precaution should be taken to prevent the zinc chloride which is highly deliquescent kfrom absorbing water from the atmosphere, which has a detrimental effect on the mixture, although a negligible amount of water may be :absorbed by the Vzinc chloride when adding it to the zinc oxide and lacetone.

The zinc chloride combines with the zinc oxide when The dissolving of the zinc oxide by the zinc chloride substantially reduces the size of the particles of the zinc oxide. The zinc oxide Iand zinc chloride act as reagents or decomposing aids when the coating is engaged by the heating stylus, and reducing the zinc oxide to an extremely small particle size establishes a more intimate physical contact 'between the molecules of the zinc oxide land zinc chlloride ,and of the {polyvinylidene chloride thus greatly enhancing the decomposition or carbonization of the coating Iand providing the most effective results when the coating is ydecomposed or lcarbonized by the heating stylus.

The zinc chloride, zinc oxide, and acetone are preferably mixed in a suitable mill until a uniform mixture is formed, and the mixture is then milled for a suicient length of time to reduce the size of the zinc oxide particles which vwere not reduced by the zinc chloride which, as above Imentioned, enhances the action of these materials to aid the decomposition or carbonization of the coating. The milling time can vary depending upon the mode of milling and the particle size desired. Milling in a conventional ball mill for twenty-four hours would be sufficient.

The copolymer of vinylidene chloride and acrylonitrile is then added to the mixture and the mixture is then The mixture is placed on the base sheet C to be coated as soon as possible after formation. The coating is applied in a manner to completely cover the surface of the material, filling all surface recesses and providing a smooth uniform coating in intimate contact with the surface, avoidin-g air Applying the coating mixture to the base sheet is simplified because the coating mixture is smooth and uniform, free of lumps, and because of the nature of the `solvents used which areeasily absorbed by the base sheet C. The coating is then dried for an adequate length of time at temperatures under 200 F. The drying operavtion evaporates the acetone from the mixture and the are connected to a source of electrical energy and thus anV electrical current is caused to flow through the blank A when the stylus B engages the heat sensitive coating 12. This current How heats the coating 12 and causes it to decompose or carbonize in the area Where the stylus engages the coating, which results in a clear, sharp mark on the blank. Other heating styluses, of course, could be used to provide a mark which do not cause a current to liow through the blank A, but alternatively heat the coating 12.

' Such heating styluses could be used in the absence of any conductive materials in the blank A. Y

The decomposing aidsor reagents used in the preferred 1 embodiment function when the coating is engaged by the heating stylus to aid in the thermal decomposition of the f fcoating 12. Moreover, if a zinc plate is used as the base material, it also aids in the decomposition of the coating and thus -greatly enhances the marking of the blank.

Preferably, as above noted, a combination of Zinc chloride and zinc oxide are used as reagents. This combination gives the coating a white appearance which is Whiter than would be achieved if zinc oxide were used alone. Since the copolymer of vinylidene chloride is clear in color, the zinc chloride and zinc oxide comprise a means providing a color to provide a contrast between a mark formed thereon and the coating, for without the zinc chloride or zinc oxide or some other means for providing a contrast, the coating Would be clear and there would be little contrast to aid the visual observance of the mark on the blank. Thus a mark on the coating in such asituation would be diiiicult to discern, whereas a mark on the coating which includes a contrast between the mark and the coating is extremely clear, particularly when the coating has a white appearance, which highlights the mark formed by decomposition of the coating. It should be clear that byvarying the amounts of zinc oxide, zinc chloride and polyvinylidene chloride in the mixture, the contrast can be varied.

As above noted, the rea-gents including zinc oxide and zinc chloride provide the desired contrast, however, this contrast may bev provided by other additives, including pigments, or by the so-called blush effect. As an alternative to the use of zinc oxide, other metal oxide pigments may be used, such as titanium dioxide and which when added to zinc chloride are dissolved thereby. Such metal oxide pigments will affect the decomposing action of the coating somewhat differently than the Zinc oxide and to certain extents may be more desirable. For example, the titanium dioxide when used greatly reduces the corrosive fumes which are created by the decomposition of the coating including zinc oxide.

The blush effect, of course, as is Well known, provides a cloudy white appearance -on the coating which results from the condensation of moisture out of the air into the film and the subsequent cooling of the film surface. Normally, of course, this is undesirable but it can be utilized to provide the necessary contrast in the coating of the present invention. This blush effect can also be provided by the addition of a small amount of other solvent less volatile than acetone or the solvent used in the mixture that in turn has no ainity with it.V

While the above descrip-tion has discussed the desirability of using zinc chloride and zinc oxide as reagents, it should be understood, of course, that other decomposing aids or reagents may be used, suoh as iron and copper base materials. Furthermore, rather than using zinc chloride along with zinc oxide, other zinc halides might be used including zinc iodide and/or zinc bromide as substituents for the zinc chloride.

The coating material formed by the formula set forth in the above table has been decomposed in an oven at approximately 212 F. in one minute and at approximately 365 F. in one second. It should be readily apparent, therefore, that a stylus would provide instant marking since a stylus would be capable ofy heating the coating to 212 F. instantly. 'Ihese relatively low temperatures permit the use of stylus or pen velocities in` excess of those in the prior art known to applicant, leaving a markedly visible trace. Also, the coating decomposes before it melts and thus the coating does not melt and does not blur or smear the line formed by the heating stylus, and thus an extremely sharp and clear mark results. The fact that the temperature at which the coating 'is marked is relatively low results in the heat being limited to the area beneath the stylus. Moreover, since the pen velocity is relatively high, an even -sharper and clearer mark results. Furthermore, there is no sticking of the stylus or pento the coating creating a drag on the stylus. Also, at the relatively lowrtemperatures the base to which the coating is applied will not burn.

Thus it can be seen that the vinylidene chloride coating when engaged lby the stylus B is quickly decomposed and forms a smooth line in the area where the stylus engages the coating and permits the stylus to travel at a relatively high velocity. The line formed by the stylus is sharp and clear when contrasted with the relatively rough and jagged lines formed on prior art blanks. Also, since the vinylidene chloride coating is highly resistant to acids, moisture and abrasive action the blank A is of a more permanent nature and has Ia greater storage life than the prior art blanks.

While the blank shown in the drawings is of a flat coniiguration it should be noted thatthe blank could be of any desired configuration kto conform with the requirements of the machine or .apparatus which is being used to mark the blank. For example, a drum or similar configuration could be used.

While the preferred embodiment of the presen-t invention has been described in considerable detail hereinabove, it should be understood that certain changes and modifications thereof may be made by those skilled in the art, and that the invention is not intended to be Ilimited to the specific embodiments described, but is intended to cover all changes coming within the scope of the appended claims.

Having described my invention, I claim:

1. A blank for receiving visual intelligence on Iselected areas comprising a base 'material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one surface portion and in intimate adhered contact with said'one `surface portion, said coating being a nonpowdery cohesive mass of material `decomposable by heating above 212 F. and comprising a Y copolymer of vinylidene chloride and acrylonitrile and Zinc oxide and zinc chloride reagent materials which aid in the decomposition of said copolymer, with the proportion by weight of the reagent material to the copolymer being about 21/2 to 1 and the proportion by Weight of zinc oxide to zinc chloride being about 4 to 1.

2. A blank for receiving visual intelligence on selected areas comprising an electrical current conducting base material having two planar surface portions, one of said surface portions having a smooth uniform coating dr-ied thereon and substantially covering said one surface portion and in intimate -adhered contact with said one surface portion, said coating being a nonpowdery cohesive mass of material which decomposes and changes in color in the area Where an electrical potential is applied thereto and comprising a copolymer of vinylidene chloride and acrylonitrile and zinc oxide and zinc chloride reagent materials which aid in the decomposition of said copolymer, with the proportion by weight of the reagent l material to the copolymer beingiabout 21/2 to 1 and the proportion by weight of zinc oxide to zinc chloridebeing about 4 to 1.

3. A blank for receiving visual intelligence on selected areas comprising a base material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one surface portion and in intimate adhered contact with said one surface portion, said coating being a nonpowdery cohesive-mass of material decomposable by heating above 212 F. -and comprising a material selected from the group comprising polyvinylidene chloride anda copolymer of vinylidene chloride and acrylonitrile and zinc oxide and zinc chloride reagents which aid in the decomposition of'said materal, with the proporton by Weight of the reagents to said material being within the ratio range of 5/4 to 5/1 and the proportion by weight of zincroxide to zinc chloride being within the ratio range of 8/ 1 to 2/1.

4. The blank receiving visualintelligence on selected areas as defined in claim 3 wherein said base material 5. A blank for receiving visual intelligence on selected i areas comprising a base material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one :surface portion and in intimate adhered Contact with said one surface portion, said coating being a nonpowdery cohesive mass of material decomposable by heat'mg above 212 F. and comprising a material selected from the group comprising polyvinylidene chloride and a copolymer of vinylidene chloride and acrylonitrile, zinc chloride reagent which aids in the decomposition of said material, and a metal oxide pigment which is dissolved when mixed with zinc chloride with the proportion by weight of the reagent and pigment to'said material being within the ratio range of 5 4 to 5/ 1 and the proporion by weight of the pigment to the zinc chloride being within the ratio range of 8/1 to 2/ 1.

6. A blank for receiving visual intelligence on selected areas comprising a base material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one surface portion and in intimate adhered contact with said one surface portion, .said coating being a nonpowdery cohesive mass of material decomposable by heating above 212 F. and comprising a material selected from the group comprising polyvinylidene chloride and a copolymer of vinylidene chloride and acrylonitrile, zinc chloride reagent which aids in the decomposition of said material, and titanium dioxide with the proportion by weight of the zinc chloride and titanium dioxide to said material being within'the ratio range of 5/ 4 to 5 l and the proportion by weight of the titanium dioxide to the zinc chloride being within the ratio range of 8/1 to 2/1.

7. A blank for receiving visual intelligence on selected areas comprising a -base material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one surface portion and in intimate adhered contact with said one surface portion, said coating being a nonpowdery cohesive mass of material decomposable by heating above 212 F. and comprising a materialselected from the group comprising polyvinylidene chloride and a copolymer of vinylidene chloride and acrylonitrile and zinc oxide and a zinc halide as reagents which aid in the decomposition of said r'naterial, with the proportion by weight of the reagents to said material being within the ratio range of 5/4 to 5/1 and the proportion by weight of zinc oxide to zinc halide being within the ratio range 8. A blank for receiving visual intelligence on selected areas comprising a base material having two planar surface portions, one of said surface portions having a smooth uniform coating dried thereon and substantially covering all of said one surface portion and in intimate adhered contact with said one surface portion, said coating being a nonpowdery cohesive mass of material decomposable by heating above 212 F. and comprising a material selected from the group `comprising polyvinylidene chloride and a copolymer of vinylidene chloride and acrylonitrile, a halide of metal selected from the group comprising zinc, iron and copper which aids in the decomposition of said material and a metal oxide pigment which is dissolved when mixed with the metal halide.

References Cited by the Examiner 2,855,266 10/1958 James l17-36.8X

WILLIAM D. MARTIN, Primary Examiner. H. W. MYLIUS, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2735784 *30 Jul 195321 Feb 1956 Process of electrostatic printing
US2735785 *30 Jul 195321 Feb 1956 Process of electrostatic printing
US2855266 *16 Feb 19537 Oct 1958Little Inc AHeat sensitive materials for recording instruments
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3411948 *8 Apr 196419 Nov 1968Hewlett Packard CoElectrosensitive recording medium
US3511973 *27 Dec 196512 May 1970Sperry Rand CorpThermo-resistive recording technique
US3831179 *18 Dec 197220 Aug 1974Bosch Gmbh RobertElectrographic tape recording medium
US3867169 *14 Aug 197218 Feb 1975Mitsubishi Paper Mills LtdNon-carbon copying upper paper
US3940864 *25 Mar 19742 Mar 1976Contemporary, Inc.Plastic plates adapted to be imprinted and methods of manufacturing and imprinting on plastic plates
US4166144 *6 Oct 197828 Aug 1979Dennison Manufacturing CompanyElectrosensitive metalized label stock
US4252601 *5 Jun 197824 Feb 1981La CellophaneOrganic styrene resin pigment particles dispersed in polyvinylidene chloride binder, solvent
US4456632 *16 Dec 198226 Jun 1984Dennison Manufacturing CompanyWhite electrosensitive paper
US4781941 *3 Apr 19851 Nov 1988Fuji Photo Film Co., Ltd.Method of matting pre-sensitized plates
US5562994 *21 Sep 19948 Oct 1996Kimberly-Clark CorporationUn-coated paper-making sludge substrate for metallizing
US85360875 Apr 201117 Sep 2013International Imaging Materials, Inc.Thermographic imaging element
DE1671571B1 *18 Aug 19678 Jul 1971Phonocopy IncElektrothermographisches aufzeichnungsverfahren und dabei verwendeter schichttraeger
Classifications
U.S. Classification428/463, 346/135.1, 428/464, 428/913, 347/221
International ClassificationB41M5/36
Cooperative ClassificationB41M5/36, Y10S428/913
European ClassificationB41M5/36